Cathode-ray tube containing cerium activated yttrium silicate phosphor

ABSTRACT

A flying-spot scanner or a color television tube having indexing strips comprises a luminescent screen or indexing strips of a substantially non-persistent luminescing material consisting of yttrium silicate activated by trivalent cerium.

United States Patent 1191 De Mesquita et al. 1 1 Feb. 6, 1973 [54] CATHODE-RAY TUBE CONTAINING [56] References Cited CERIUM ACTIVATED YTTRIUM SILICATE PHOSPHOR UNITED STATES PATENTS W51 Albert comes w 5'181'332 3/323 3132????11331131: ""iiiifil'i? Alfred both of Emma-8mg; 3,523,091 8/1970 McAllister ..252/3014F Emdhoven, Netherlands 3,250,722 5/1966 Borchardt ....2s2/301.4 R

[ Assigneez Us. ps Corporation New 3,481,884 12/1969 Pal1lla ..252/301.4P

Y r 1 OTHER PUBLICATIONS Filedi g- 1969 Peters, Cathodoluminescent Lny (Si 611K715 Phos hors Journal of Electrochemical Societ Vol.

I l.N .2 84 179 P y [2 1 APP 117, No. 7, July l969,pages 985-988.

. P Eita -Robert D. Edm nds [30] Foreign Application Priority Data ';ZZ-$-g g7 i c z 0 Aug 9, 196i; Netherlands 6 [57] A S C [52] US. Cl. ..313 /92 PH, 252/3014 F A flying-spot scanner or a color television tube having [51] Int. CI... ..C09k 1/54, HOlj 29/20 indexing strips comprises a luminescent'soreen or in- [58] dexing strips of a substantially non-persistent lu- Field of Search ..252 301.4 Fv

minescing material consisting of yttrium silicate activated by trivalent cerium.

8 Claims, 2 Drawing Figures PATENTEUFEB 6 I975 Mnm) INVENTORS ALBERT H.G. DE MESQUITA Algal HRH? Agent CATIIODE-RAY TUBE CONTAINING CERIUM ACTIVATEDYTTRIUM SILICATE PHOSPI-IOR The invention relates to a cathode-ray tube provided with a luminescent screen and to a luminescent material for use in'such a screen.

Cathode-ray tubes provided with a luminescent screen which emits radiation upon excitation by the electron beam generated in the tube are used for many purposes, for example, for displaying television images in color or in black and white, for recording oscillograms and for flying-spot scanners. Dependent on their use, the materials to be used in the luminescent screens must have different properties, for example, as regards spectral energy distribution, energy conversion efficiency, saturation, etc. A property which is always desired is of course that the energy conversion of the impinging electrons into radiation is effected at a high effi'ciency.

For'sorne uses, for example, in flying-spot scanners a paramount factor is the decay time of the radiation of the luminescent material. In this respect and in the description following hereinafter the decay time is understood to mean the time during which the intensity of the radiation emitted by the luminescent material, after 1 discontinuation of the electron bombardment,

decrease to He the value of the intensity just before I which the luminescent screen is excited moves in such scanners in accordance with a given pattern, sometimes also called raster, across the luminescent screen. Unlike the, electron beam in television display tubes, the

' electron beam is then not modulated. As a result a fast moving luminous spot of constant intensity is produced on the luminescent screen. The light from this moving luminous spot is projected on a document to be disp layed,- for example, a lantern slide, a film or a security paper and is partly transmitted or reflected thereby.

Thetransmit'ted or reflected light is directed on a photo-cell in which it .is converted into an electrical signal. This electrical signal may then be transmitted with the aid of known communication means-to a device in which a picture of the transmitted document I is formed.

In the flying-spot scanner, the requirement must be imposedthat the radiation incident on the photocell is exclusively correlated with the optical absorption at the area ofthe spot of the documents which must be displayed at that moment. This gives rise to therequirement that the decay time of the luminescent radiation relative to the time of the electron beam remaining at a given area must not be long. If, as is very common practice, the scanning speed of the luminescent screen is equal to the speed at which a normal television display screen is scanned, this leads to the requirement that the decay time must be smaller than approximately 10' sec.

, Aplurality of luminescent materials has been found which satisfy this requirement and which have in addition a fairly high conversion efficiency. One of these substances, which is frequently used, is the, so-called gehlenite, (composition Ca,Al,SiO which is activated by trivalentv cerium. The maximum emission of this material upon excitation by'electrons lies at approximately4l0nm. d

2.10 and 5.10" sec., they have a high conversion effi- For reasons similar to those as described above, a luminescent material having a very small decay time is' also desired for use in the so-called indexing strips in indexing cathode-ray tubes which serve to display colored-images, for example, colored television images. In these tubes the picture display screen comprises strips having materials luminescing in different colors from which the picture to be displayed is composed. These strips, which generally emit red, green and blue light, are provided on the screen in so-called triplets. As is known it is necessary for the picture display screen to be scanned very accurately for displaying colored images with the aid of a cathode-ray tube. This means that the area where the electron beam is incident on the screen at a given instant must exactly be a photo-cell mostly located outside the tube and converted in this cell into an electrical signal which is applied to the circuit arrangement which effects the scanning movement of the electron beam and stabilizes 7 this movement.

The light originating from the strips of luminescentmaterial of the triplets may of course not influence the scanning circuit. Consequentlya photo-cell or a combination of a photo-cell and a filter is used which is insensitive to the radiation emitted by the triplets. A luminescent: material which only emits radiation of shorter wavelengths than the light from the triplets is mostly used in the indexing strips; the maximum of this radiation lies preferably between 350 .and 400 nm. Radiation .of wavelengths shorter than 350 nm. cannot generally pass the glass envelope of the tube and thus does not reach a photo-cell located outside the tube. 7

Until now the gehlenite already referred to above has preferably been used also for the indexing strips, although the maximum emission thereof is actually slightly too high, namely at approximately 410 nm.

Although it had been realized that a very short decay time is necessary for both flying-spot scanners and for indexing display tubes, it had so far not been considered that a luminescent material of the desired short decay time, for example, gehlenite may sometimes still emit a considerable amount of radiation after the in-v su-oi zu v oun) wherein p has the value of l or 2, and

The materials which satisfy the above given formula and conditions have a decay time which lies between ciency and are only very slight persistent. v

The maximum of the emission of a material wherein p= 1 lies between approximately 400 and 460 nm. This material will preferably be used in tubes for flying-spot scanners,j particularly when transmitting colored images and will not be used. in indexing display tubes.

For that purpose the material wherein p 2 which has a maximum: emission between approximately 360 and 400 nm is more suitable.

The cerium content expressed by the factor of q hasv some influence on the conversion efficiencyand on the persistence phenomenon. The shortest persistence times and the highest efficiencies are both obtained'if 10 E q g 5.10

This maybe evident. from the following tables.

It may serve for comparison that the conversion efficiency 'r of gehlenite having acerium content of 0.04 is approximately 5 percent and the persistence is 5 to percent. v

The percentage of persistence is measured as follows.

The material to be measured is provided on the screen of a cathode-ray tube and excited in a'repeating manner therein by means of an electron beam which is modulated by a signal giving the beam its full intensity for microseconds and entirely suppressing the beam for 80 subsequent microseconds. The light emitted by the luminescent materialis measured withthe aid of a photo-cell after a given period to stabilize the material in its excited condition. Tables I and [I show the ratios of the intensity after 100 sec. and that after 20 p. sec.

The inventionwill now bedescribed with reference to a drawing and two examples showing preparation of luminescent materials for use in tubes according to the invention. I

FIG. 1 of the drawing diagrammatically shows a cathode-ray tube according to the invention.

FIG. 2 of the drawing shows in a graph the spectral energy distribution upon excitation by electrons of the materials prepared in accordance with the examples mentioned below.

EXAMPLE I.

A mixture was made of 1.474 gms of hydrated SiO, (siO -content 89.5 percent) 0.l46 gms ofYF;

0.066 gms of C e=0 2.099 gms of Y O and this mixture was fired for 4 hours at a temperature of approximately l,400C in a mixture of 50 percent of C0546 percent of N and 4 percent of I*I,. The reac-v tion product obtained was homogenized and once more tired in the same. manner. Subsequently the reaction product was again homogenized and fired in the same gas atmosphere for 4 hours at a temperature of approximately 1 ,600C. The reaction product obtained was puven'zed, sieved if necessary and it .was then ready for use in-the screen of a cathode-ray tube according to the invention.

The luminescent material obtained satisfies the formula Y ma om z v As is evident a'slight excess of SiO was used during the preparation so as to enhance the course of the reaction. The efficiency of the material has 4 percent and the persistence was approximately 0.6 percent.

- EXAMPLE n.

The luminescent material obtained satisfies the for-- mula ms om rv The efficiency of the material was 6 percent and the persistence was less than 0.1 percent.

Known methods may be used for-providing the luminescent materials in the screen of the cathode-ray tube. A mixture of a material wherein p l and a material wherein p 2 can sometimes be used.

In FIG. 1 of the drawing the envelope of the cathoderay tube is indicated by 1. The window is indicated by 2 whose inner side is coated with a luminescent screen 3 comprising a luminescent material as described above.

' FIG. 2 of the'drawing shows a graph in which the wavelength A is plotted in nm on the abscissa and the emitted energy is plotted on the ordinate in arbitrary 1. A trivalent cerium activated luminescent yttrium silicate consisting essentially of a solid solution corresponding to the formula zu-m zc v tsnp) wherein p is l or 2 and 2. The luminescent silicate of claim 1 wherein g q=5.10'

3. The luminescent silicate of claim 2 wherein p l.

v 6 phosphor of the formula zu-o zo v wnm wherein p is 1 or 2 and 2.10 g q 2.10- 6. The cathode-ray tube of claim 5 wherein 10' E q 5.10

7. The cathode-ray tube of claim 6 wherein p l. v 8. The cathode-ray tube of.claim 6 wherein p 2.

' a: :u a: a 

1. A trivalent cerium activated luminescent yttrium silicate consisting essentially of a solid solution corresponding to the formula Y2(1 q)Ce2qSipO(3 2p) wherein p is 1 or 2 and 2.10 4 < or = q < or = 2.10
 1. 2. The luminescent silicate of claim 1 wherein 10 3 < or = q 5.10
 2. 3. The luminescent silicate of claim 2 wherein p
 1. 4. The luminescent silicate of claim 2 wherein p
 2. 5. A cathode-ray tube, comprising a discharge tube having a vacuum tight envelope, an electron gun provided within said envelope for producing an electron beam and a luminescent screen capable of being excited by said electron beam, said luminescent screen containing a trivalent cerium activated yttrium silicate phosphor of the formula Y2(1 q)Ce2qSipO(3 2p) wherein p is 1 or 2 and 2.10 4 < or = q < or = 2.10
 1. 6. The cathode-ray tube of claim 5 wherein 10 3 < or = q 5.10
 2. 7. The cathode-ray tube of claim 6 wherein p
 1. 